Diazotype reproduction material



DIAZOTYPE REPRODUCTION MATERIAL Filed March 19, 1963 HEAT- DEVELOPAB LETWO-COMPONENT PHOTOSENSITIVE DIAZOTYPE FIG. I LAYER I2 SUPPORT I I HEAT-DEVELOPABLE TWO- COMPONENT PHOTOSENSITIVE DIAZOTYPE REPRODUCTIONMATERIAL IO TWO-COMPONENT PHOTOSENSITIVE DIAZOTYPE LAYER 23 PRECOATLAYER 22 FIG. 2

SUPPORT 2| HEAT-DEVELOPABLE TWO-COMPONENT PHOTOSENSITIVE DIAZOTYPEREPRODUCTION MATERIAL 20 FIG 3 HEAT-ACTIVATABLE DEVELOPING AGENT 32SUPPORT 3| DEVELOPING SHEET3O HEAT-ACTIVATABLE DEVELOPING AGENTTWO-COMPONENT TWO- COMPONENT PHOTOSENSITIVE PHOTOSENSITNE DIAZOTYPELAYER 42 D|AZOTYPE SUPPORT 4| REPRODUCTION MATERIAL 4O INVENTOR. THOMASKASH I W A BA RA ATTO NEY United States Patent 3,189332 DIAZOTYPEREPRODUCTION MATERTAL Thomas T. Kashiwabara, Fort Lee, N.J., assignor toKeuli'el & Esser Company, Hohoken, N1, a corporation of New Jersey FiledMar. 19, 1963, Eer. No. 266,332 20 Claims. (Cl. 96--49) This inventionrelates to diazotype reproduction materials and methods for theirproduction and use, and refers more particularly to two-componentphotosensitive diazotype reproduction materials which are developable bymeans of heat,'and to the methods and means for accomplishing the heatdevelopment of said materials Photosensitive diazotype materials arewell known andhave many advantages over other means of reproduction whenconsider-ing the combined basis of quality and cost. The photosensitivediazotype materials, however, possess some inherent disadvantagesdepending upon their type. -,There are two generaltypes ofphotosensitive diazo systems and materials based 'on the means ofdevelopment: the two-component diazotype materials using the dry methodof diazo development; and the one-component diazotype materials usingthe semi-wet method of diazo development.

The dry diazo materials utilize gaseous ammonia to raise the pH of thecoating after exposure to allow coupling of the diazo compound andcoupler which are coated on the same support. The obvious disadvantageof this system is that it requires the use of gaseous ammonia which isobnoxious and dangerous to handle, and

which requires exhaust equipment in order to be utilized in confinedspaces;

The semirwet system of diazo development utilizes a photosensitivematerial which comprises a base sheet and a coating of photosensitivediazo compound coated on the base sheet. After exposure under a masterto actinic light, the sheet coated with the diazo compound is passedthrough a chemical bath which contains an alkali and a coupler todevelop the image by dye formation. Among the major disadvantages ofthis method is that a liquid is required in the development step. Theliquid affects the paper base and requires drying.

Among the old attempts at producing a heat-developable reproductionmaterial was one which utilized a base sheet having a dark background onwhich a layer of a light-colored wax was applied, The master was placedagainst the wax layer and was exposed to infra-red radiation which wasconverted in the image areas to heat which then passed by conduction tothe wax layer. The wax layer melted under those portions of the masterwhich contained an image and allowed the dark back ground of the basesheet to be seen, which in effect reproduced the master image. Thedisadvantages of this system of reproduction were cost as compared tothe conventional diazo systems, quality inferior to the diazo product,and retained heat sensitivity.

The old systems used melting wax layers and the like inheat sensitiveand not necessarily light sensitive materials.

For many years heat development of photosensitive ,clia zo materials hadbeen tried without noteworthy success It had been attempted in order toeliminate. the disadvantages of gaseous ammonia in the dry developingsystem, and liquid developer in the semi-wet system.

The development of exposed two-component diazotype prints by gases givenoff by the decomposition of ammonia compounds from a developing sheetunder the infiuence of heat had' been tried. The ammonia compounds foundto be particularly suitable for development of diazotype prints were theproducts of ammonia and weak acids. Good results wereobtained fromammonium carbonate,

ammonium bicarbonate, and'the like, which decompose freely attemperatures slightly above room temperature with the release of freegaseous ammonia and water vapor. The solid carbonates were. heated injuxtaposition to the exposed two-component diazotype paper to fullyutilize thereleased gaseous ammonia on the exposed surface. This knownmaterial had the great disadvantage of very poor shelf life'whichseverely limited its practical use.

Another known material incorporated urea with a photosensitive diazoic.The ureadecomposed with the heat and liberated ammonia gas whichneutralized and acid formed during coupling thereby aiding the'couplingof the diazoic with its photolysis phenol. Urea in a separate stratumwas tried in another material. Developing sheets impregnated with acomposition containing one compound or a combination of compounds whichliberated the vapor of an alkali or a coupler were also tried. Anothermaterial incorporated a carboxamide such as formamide,- acetamide, urea,and methyl-urea as a humectant but not as a source of alkali ammonia.

Another material was a multilayer diazotype material comprising asupport, a layer containing. a diazo compound, a; fusible barrier layerwhich melted below the decomposition temperature of the diazo compound,and alayer containing a coupler, all coated on one side of a support.The diazotype material was placed, in contact with a master andsubjected to infrared radiation. Imagewise generation and transfer ofheat from the master to the multilayer diazotype material melted thefusible barrier. layer and permitted the diazo compound and coupler toform an azo dye.

Another object is to provide a photosensitive heat-.

developable diazotype material and system which requires neither gaseousammonia nor liquid developer for development. I

Another object is to provide a photosensitive twocomponentheat-developable diazotype'reproduction material whichisheat-developable and which is stable to further application of heat.

Another object of the present invention is to provide a photosensitiveheat-developable diazotype material which is inexpensive and whichgives'good quality diazo reproduction. i

Other objects. will be apparent fication. In the present'invention, thebase necessary for the development is produced on the diazotype materialat the time of development by thermally induced chemical or physicalconversion of a base-releasing compound. The application of heat causesthis compound to release the base necessary for the couplingreaction atthe time of development. i

It has been found that many organic nitrogen compounds are suitablesources of base for heat-developable diazo mate-rials. These compoundscan be incorporated in a sensitizing layer, in a precoat layer, or in adeveloping sheetdepending upon solubility and compatibility. Thecompounds ot the present invention are induced by elevated temperaturesto release a base which increases the alkalinity of "the system andpermits coupling to take place, thereby developing the latent image.

The organic nitrogen compounds suitable for use in the present inventionare those cor-responding to the following general formula and. saltsthereof: a i

. RINHR2 wherein R [and R are members selected from the groups from thefollowing speciconsisting of: group A where R is a member selected fromthe group consisting of alkyl, hydroxyalkyl, ethoxycarbonyl alkyl,carboxyalkyl, carboxy carbamoyl alkyl, guanyl, arylguanyl, aminoguanyl,diallylamino-triazinyl, arylamino triazinyl, thiazoly-l, andpyridyl,and. R is a member selected from the group consisting of hydrogen,alkyl, and guanyl; and group B WHIBH'RL and R are members of the sameheterocyclic ring.

One sub-generic group of chemicals is that corresponding to the generalformula and salts thereof:

, guanidine (as the bicarbonate salt), phenyi 'guanidine (as thecarbonate salt); phenyl biguanide, vN; N-diallylmelamine, 2,4-diamino6phenyl-s triazine, '2-am'inothiazole, and '2-aminopyridine.

Another sub-generic group is that corresponding to the following generalformula:

wherein R and R are members of the same heterocyclic ring. .This groupincludes imid-azole, benzimidazole, and piperazine (as the hexahydrate).

' In the drawings: a

FIGURE 1 is a sectional v-iewof a heat-developable two-componentphotosensitive .diazotype reproduction material 10 comprising a support:11 and a heat-developable two-corrip0nent photosensitive diazotypelayer 12 coated on said support;

FIGURE 2 is a sectional view of a heat-developable two-componentphotosensitive diazotype' reproduction material 20 comprising a support21, aprecoat. layer 22 coated on said support, and a two-componentphotosensitive diazotype layer 23 coated over said precorat layer onsaid support; and

FIGURE. 3 is asectional view of a developing sheet 36 comprising asupport 31 and "a heat-activatab'le developing agent 3'2 impregnated insaid-support. The developing sheet is in contact with a twocomponent'photosensitive diazotypereproduction material 40 comprising asupport 41 and atwo-com ponent photosensitvie diazotype layer 42' coatedon said support; One method of the present invention for thepreparationof a heatdeveloping reproduction material is to treat a support materialwith a solution of heat-activatable developing agent. After drying, thesame support is coated on the same side or on the opposite side with asensitizing solution comprising diazonium compound and couple-r. Thecoating is dried; In this method the heatactivatable developing agent isin the first or precoat layer. The sensitized support is exposed througha master to actinic radiations and is then developed by heat in therange between the activation temperature of the developing agent. andthe scorching temperature of the support material. The heat-activatedlibenation of developing agent then causes the image to develop. Thepreparationand. .use-ot 'heat-developable tWo-component p'hotosensitivediaz-otype reproduction material precoated with heat-tactivatabledeveloping agent of the present invention is illustrated in Example 5.

In another method of preparation-of the present invention, theheat-activatalble developing agent is incorporated into the sensitizingwith the photosensitive solution comprising diazonium compound andcoupler. The solution is applied to a supportand then dried. Thesensitized support is exposed through a master to actinic radiations andafter exposure, heat is applied to the support. The temperature ispreferably in range between the activation temperature. .of thedeveloping agent and the scorching temperature of the support material.-This method of preparation is illustrated in Example 3,

A developing sheet is prepared by impregnating a support with a solutionof -il1eat-activ.atable developing agent in a suitable solvent. Thesolvent is then removed by drying. The developingshee-t is used todevelop an exposed two-component photosensitive diazotype. reproductionmaterial by placing it in face-to-fiace contact with the exposedsensitized surface of the diazotypc material and subjecting the assemblyto heat in the range between the activation temperature oftheqdeveloping agent and the scorching temperature of the diazotypesupport. This activates the developing agentand permits coupling tooccur on the sensitized surface of the diazotype material. Thepreparation and use of a developing sheet utilizing the heat-activatahledeveloping agentof the present invention is illustnalted in Example 1. 1

The developing temperature range is determined by two factors: first,the activation temperature of'the heatactivatable developing agent; andsecond, the scorching temperature of the diazotype support material. Theactivation tempenature is that degree of heat necessary to release orliberate the developing agent in the amount required for development ofa two-component photosensitive diazotypereproduction material. Thescorching temperature is that degree'of heat which darkens thebackground of a developed diazotype'print or which causes undesirablephysical degradation 'of'the diazotype support material.. V p

The examples herein are given for purposes of illustration, and it .isto be understood that the invention is not limited to these examples.

EXAMPLES G. Ethanol -Q 90 Dodecylamine 10 The prepared developing sheetwas used to heat-develop ing sheet was used to heat-develop a diazotypereproduction material by placing it in contact with the sensitizedsunface of the reproduction materialthat had been exposed toactinic-radiations through .a master; heating the developing sheet for afew seconds at C. while in contact with thesensitized surfacerof thereproduction material to release the base and thus eifect coupl ing,.and' dinally, sepa-ratingthe developing sheet from the diazo typereproduction material. A colored dye image-was formed on the diazotypereproduction material.

Tetradecylamine, hexladecylamine, ootadecylamine, 2- amino thiazole,Z-aminopy-ridine, and benzim'idazole were used in place of thedodecylamine to produce the same result. 1

Example 2.N-methyl glucamine was :used from a 10% aqueous solution toprepare a developing sheet as in Example, 1. Used in the same manner toheat-develop a diazotype reproduction material, the same results wereobtained.

Example 3.-N-methyl 'glucamine was used as a sen- G. Water 150 Tartaricacid A Trichloroacetic acid 7 1,3,6-naphthalenetrisulfonic acid, sodiumsalt 6 N-methyl glucamine 5 p-Dimethylamino benzene diazonium chloride,

zinc chloride salt 4 2,3-dihydroxy-naphthalene-G-sulfonic acid,

sodium salt 5 Thiourea 7 Zinc chloride 4 This was coated on a supportand dried. After exposure to actinic radiations through a master, thesensitized support was heated at atemperature between the melting pointof the N-rnethyl glucamine and the scorching temperature of the support.A blue image corresponding to the master image was produced.

Imidazole, n-butylamine hydrochloride, L-glutamine, glycine ethyl esterhydrochloride, phenyl biguanide, aminoguanidine sulfate, guanidineacetate, and phenyl guanidine carbonate were used in place of N-methylglucamine. Aminoguanidine bicarbonate was used in. half quantities. Allproduced a blue image with the exception of aminoguanidine sulfate whichproduced a red-violet image.

Example 4.-N,N-diallyl melamine was used in a precoat layer coated fromthe following solution:

Dioxane ml 100 N,N-dia1lyl melamine g 20 The precoated support was thencoated with the following sensitizing solution:

G. Water 150 Tartaric acid /2 Trichloroacetic acid 51,3,6-naphthalenetrisulfonic acid 6 p-Dimethylamino benzene diazoniumchloride,

zinc chloride salt 4 2,3-dihydroxynaphthalene-6-sulfonic acid,

sodium salt 5 Thiourea 7 Zinc chloride 4 After the sensitized supportwas dried, it was exposed to actinic radiations through a master andthen heat-developed for a few seconds at 150 C. to produce a blue imagecorresponding to the master image.

Example 5.-2,4-diamino-6-phenyl-s-triazine was used from a saturatedsolution in dioxane to prepare a precoat layer on a support. This wasthen sensitized as in Example 4 to produce substantially the sameresults when heat-developed.

Example 6.The sensitizing solution of Example 3 was prepared with 3 g.of benzimidazole in place of 5 g. of N-methyl glucamine. After a supportwas sensitized and heat-developed as in Example 3, a blue imagecorresponding to the master image was produced.

Example 7.A mixture of the following composition was used to prepare adeveloping sheet:

Percent Tetradecylamine acetate 5 Hexadecylamine acetate 30Octadecylamine acetate 65 The solution was prepared according to thefollowing formula:

Percent Ethanol 95 Amine acetate mixture 5 6 A support was impregnatedwith this solution and .then dried to produce a developing sheet. Thiswas used to heat-develop a diazotype reproduction material as in Example1 to produce a dye image corresponding to the master image.

Example 8.A sensitizing solution was prepared according to the formulain Example 3 using 15 g. alpha-alanine in placeof the 5 g. N-methylglucamine. The solution was coatedon a support and heat-developed toproduce a blue dye image corresponding to the master image.

It is apparent that the described examples are capable of. manyvariations and modifications within the scope of the presentinvention.All such variations and modifications are to be included within thescope of the present invention.

What I claim is:

1. A heat-developable diazo-type'material, which comprises:

a support resistant to the scorching effects of heat at the conditionsof thermal development; and

a photosensitivediazonium compound, a coupler therefor, and aheat-activatable developing agent coated on said support, said agenthaving the general formula:

.where R and R are members selected from one of the groups consistingof:

group A in which R is a member selected from the group consisting of:alkyl, thiazolyl, pyridyl, guanyl, and triazinyl, and R is a memberselected from the group consisting of hydrogen, methyl, and guanyl; andgroup B in which R and R are members of the same heterocyclic ring. 2. Amethod for making a diazo reproduction of an image, which comprises thesteps of:

exposing a diazo sheet to imagewise actinic radiation, said sheetcomprising a support resistant to the scorching effects of heat at theconditions of thermal development, and a photosensitive diazoniumcompound, a coupler therefor, and a heat-activatable developing agentcoated on said support, said agent having the general formula:

R NHR where R and R are members selected from one of the groupsconsisting of:

group A in which R is a member selected from the group consisting ofalkyl, thiazolyl, pyridyl, guanyl, and triazinyl, and R is selected fromthe group consisting of hydrogen, methyl, and guanyl; and group B WhereR and R are members of the same heterocyclic ring; and

heating said sheet at a temperature between the activation point of saidagent and the scorching point of said support to form a dye image onsaid sheet.

3. A sheet in accordance with claim 1 in which said agent is intimatelyadmixed with said diazo layer.

4. A sheet in accordance with claim 1 in which said agent is coatedbetween said support and said diazo layer.

5. A method in accordance with claim 1 in which said agent is intimatelyadmixed with said diazo layer coated on the same support.

6. A method in accordance with claim 1 in which said agent is coated onsaid support between said support and said diazo layer.

7. A material in accordance with claim 3 in which said agent isn-butylamine hydrochloride.

8. A material in accordance with claim 3 in which said agent is N-methylglucamine.

9. A material in accordance with claim 3 in which said agent is phenylbiguanide.

10. A material in accordance with claim 3 in which said 12. A materialin accordance with claim 4 in which said agent is N,N-diallyl melamine.

13. A material in accordance with claim 4 in said 'agent is2,4-diamino-6-phenyl-s-triazine.

14. A method in accordance with claim said agent is n-butylarninehydrochloride.

15. A method in accordance with calim said agent is N-methyl glucamine.

16. A method in accordance with claim said agent is phenyl biguanide.

17. A method in accordance with claim said agent is guanidine acetate. I

18. A method in accordance with claim said agent is imidazole.

19. A method in accordance with claim said agent is.N,N-diallylmelamine.

20. A method in accordance with claim said agent is2,4-diamino-6-phenyl-s triazine.

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UNITED STATES PATENTS Sprongerts 96-91 6/ 31 1/49 Greig 96-91 3/51 Duerr96-75 4/52 Neumann et a1 96-91 11/52 Reichel 96-49 2/54 Lindquist117-154 XR 1/ 56 Morrison 96-49 12/56 Marron et al. 96-49 2/58 Barrettet a1; 117-154 XR 7/62 Klimkowski et al 96-75 XR 9 FOREIGN PATENTS 7/59Great Britain. 11/60 France.

No. 4, July August 1961, pp. 239-243. NORMAN G.-TORCHIN, PrimaryExaminer.

1. A HEAT-DEVELOPABLE DIAZO-TYPE MATERIAL, WHICH COMPRISES: A SUPPORTRESISTANT TO THE SCORCHING EFFECTS OF HEAT AT THE CONDITIONS OF THERMALDEVELOPMENT; AND A PHOTOSENSITIVE DIAZONIUM COMPOUND, A COUPLERTHEREFOR, AND A HEAT-ACTIVATABLE DEVELOPING AGENT COATED ON SAIDSUPPORT, SAID AGENT HAVING THE GENERAL FORMULA:
 2. A METHOD FOR MAKING ADIAZO REPRODUCTION OF AN IMAGE, WHICH COMPRISES THE STEPS OF: EXPOSING ADIAZO SHEET TO IMAGEWISE ACTINIC RADIATION, SAID SHEET COMPRISING ASUPPORT RESISTANT TO THE SCORCHING EFFECTS OF HEAT AT THE CONDITIONS OFTHERMAL DEVELOPMENT, AND A PHOTOSENSITIVE DIAZONIUM COMPOUND, A COUPLERTHEREFOR, AND A HEAT-ACTIVATABLE DEVELOPING AGENT COATED ON SAIDSUPPORT, SAID AGENT HAVING THE GENERAL FORMULA: